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Cruise MSM57-1/-2 was funded by the German Research Foundation ( DFG ), the Research Center/Excellence Cluster “The Ocean in the Earth System” at MARUM–Center for Marine and Environmental Sciences, University of Bremen and funds from CAGE. This work is partly supported by the Research Council of Norway (RCN) through Petromaks2-NORCRUST (project number 255150 ) and the Centre of Excellence funding scheme for CAGE (project number 223259 ). APF’s contribution was part of the SEAMSTRESS project supported by starting grants from the Tromsø Research Foundation and the Research Council of Norway (grant nr. 2878659 ). Seafloor seepage sites along the Vestnesa Ridge off west-Svalbard have been, for decades, a natural laboratory for the studies of fluid flow and gas hydrate dynamics along passive continental margins. The lack of ground truth evidence for fluid composition and gas hydrate abundance deep in the sediment sequence however prohibits us from further assessing the current model of pockmark evolution from the region. A MARUM-MeBo 70 drilling cruise in 2016 aims to advance our understanding of the system by recovering sediments tens of meters below seafloor from two active pockmarks along Vestnesa Ridge. We report pore fluid composition data focusing on dissolved chloride, stable isotopes of water (δ18O and δD), and the isotopic composition of dissolved boron (δ11B). From one of the seepage sites, we detect a saline formation water with two layers where gas hydrates were recovered. This saline formation pore fluid is characterized by elevated chloride concentrations (up to 616 mM), high B/Cl ratios (9 × 10−4 mol/mol), high δ18O and δD isotopic signatures (+0.6‰ and +3.8‰, respectively) and low δ11B signatures (+35.0‰), which collectively hint to a high temperature modification at great depths. Based on the dissolved chloride concentration profiles, we estimated up to 47% of pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. The observation of bubble fabric in the recovered gas hydrates suggests formation during past periods of intensive gaseous methane seepage. The presence of these gas hydrates without associated positive anomalies in dissolved chloride concentrations however suggests that the decomposition of gas hydrate is as fast as its formation. Such a state of gas hydrates can be attributed to a relatively low methane supply transported by the saline formation water at present. Our findings based on pore fluid composition corroborate previous inferences along Vestnesa Ridge that fluids sustaining seepage have migrated from great depths and that the variable gaseous and aqueous phases through the gas hydrate stability zone control the distributions of authigenic carbonates and gas hydrates. Publisher PDF

Highlights • Overview on geochemical composition of pore water and solid phase of sediments on the Azores Plateau. • Evidence for deep marine hydrothermal activity on the Azores Plateau. • Pore water data suggest ongoing anaerobic oxidation of methane and carbonate recrystallization. The Azores Plateau is an active magmatic region in the Central North Atlantic Ocean. In this study, we present a comprehensive data set of major element compositions and 87Sr/86Sr ratios of pore waters from surface sediments (0–9 mbsf) of the Azores Plateau. Based on distinct geochemical signatures we can separate normal marine from hydrothermally affected sediments. Normal marine sediments can further be differentiated by their ash content. Pore waters of ash rich gravity cores (GCs) do not show any deviations from seawater values except of a minor increase in Sr. In contrast, ash poor GCs generally show a trend for decreasing Ca with increasing depth, accompanied by a minor SO4 decrease and a more pronounced Sr increase. We suggest that these deviations are caused by processes such as anaerobic oxidation of methane and carbonate recrystallization. At four additional sample locations we observed a decrease in Mg and SO4 accompanied by a Ca increase in the pore waters, a pattern typical for hydrothermal fluids. The existence of hydrothermal systems in this region are corroborated by multi-channel seismic data, suggesting that sill or dyke intrusions are present in the subsurface close to the core locations. Overall, our observations offer preliminary indications for the existence of submarine hydrothermal systems on the Azores Plateau away from the Mid- Atlantic Ridge.

The Permian/Triassic boundary approximately 251.9 million years ago marked the most severe environmental crisis identified in the geological record, which dictated the onwards course for the evolution of life. Magmatism from Siberian Traps is thought to have played an important role, but the causational trigger and its feedbacks are yet to be fully understood. Here we present a new boron-isotope-derived seawater pH record from fossil brachiopod shells deposited on the Tethys shelf that demonstrates a substantial decline in seawater pH coeval with the onset of the mass extinction in the latest Permian. Combined with carbon isotope data, our results are integrated in a geochemical model that resolves the carbon cycle dynamics as well as the ocean redox conditions and nitrogen isotope turnover. We find that the initial ocean acidification was intimately linked to a large pulse of carbon degassing from the Siberian sill intrusions. We unravel the consequences of the greenhouse effect on the marine environment, and show how elevated sea surface temperatures, export production and nutrient input driven by increased rates of chemical weathering gave rise to widespread deoxygenation and sporadic sulfide poisoning of the oceans in the earliest Triassic. Our findings enable us to assemble a consistent biogeochemical reconstruction of the mechanisms that resulted in the largest Phanerozoic mass extinction. The end-Permian mass extinction was linked with ocean acidification due to carbon degassing associated with Siberian Trap emplacement, according to boron isotopes from fossil shells and reconstruction of the carbon cycle.

Highlights • The SUGAR project has developed and tested various methods for gas production from marine gas hydrates from micro to field scale. • Numerical simulations improved the understanding of processes on molecular to reservoir scale. • Depressurization is a promising technology for exploiting gas hydrate deposits in the Danube Delta. • The injection of CO2 or CO2–N2 is not a suitable method for the exploitation of gas hydrate deposits in the Danube Delta. Abstract One important scientific objective of the national research project SUGAR – Submarine Gas Hydrate Reservoirs was the development, improvement, and test of innovative concepts for the production of methane from natural gas hydrate reservoirs. Therefore, different production methods, such as the thermal stimulation using in situ combustion, the chemical stimulation via injection of CO2 as a gaseous, liquid or supercritical phase and depressurization were tested alone or in combination at different scales. In the laboratory experiments these ranged from pore and hydrate grain scale to 425-L reactor volume, whereas numerical models were applied to describe the related processes from molecular to reservoir scale. In addition, the numerical simulations also evaluated the feasibility and efficiency of the application of these methods in selected areas, such as the Danube Paleodelta in the Black Sea, addressing the two dominant methane hydrate reservoir settings, buried channel-levee and turbidite systems. It turned out, that the injection of CO2 or a CO2–N2 gas mixture is not applicable for the Danube Paleodelta in the Black Sea, because the local pressure and temperature conditions are too close to the equilibrium conditions of both, the CO2 hydrate and a CO2–N2 mixed hydrate stability fields. Experiments using thermal stimulation and depressurization showed promising results but also some issues, such as sufficient heat transfer. In summary it can be said that the applicability and efficiency of each method has to be proven for each specific hydrate reservoir conditions. Based on the results obtained by numerical simulations the most promising and safe method for the production of CH4 from hydrate bearing sediments in the Danube Paleodelta would be the depressurization technique. This study summarizes the main experimental and modeling results.

Gas hydrate dynamics and the fluid flow systems from two active pockmarks along Vestnesa Ridge (offshore west Svalbard) were investigated through the pore fluid geochemistry obtained during the 2016 MARUM-MeBo 70 drilling cruise. Based on the pore water chloride concentration profiles from Lunde and Lomvi pockmarks, we estimated up to 47% pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. These gas hydrates were formed during periods of gaseous methane seepage, but are now in a state of dynamic equilibrium sustained by a relatively low methane supply at present. We detect a saline formation pore fluid around nine meters below seafloor from one of the seepage sites in Lunde pockmark. This formation pore fluid has elevated dissolved chloride concentrations and B/Cl ratios, higher δO and δD isotopic signatures of water and lower δB signatures, which collectively hint to a high temperature modification of this fluid at great depths. By integrating our findings with the previous work from Vestnesa Ridge, we show that the variable fluid phases (gaseous vs. aqueous fluid) and migration pathways are controlled by the sediment properties, such as buried carbonate crusts, and the state of fluid reservoirs.

Highlights • Physical properties obtained from core and log data at the Danube deep sea fan are reported. • Core-log-seismic integration defines stratigraphic framework at the S2 channel. • All data suggest no gas hydrate is present at drill sites within uncertainties of methods employed. Abstract Drilling, coring, and geophysical logging were performed with the MARUM-MeBo200 seafloor drilling rig to investigate gas hydrate occurrences of the Danube deep sea fan, off Romania, Black Sea. Three sites within a channel-levee complex were investigated. Geophysical log data of P-wave velocity, electrical resistivity, and spectral gamma ray are combined with core-derived physical properties of porosity, magnetic susceptibility, and bulk density. Core- and log physical property data are used to define a time-depth conversion by synthetic seismogram modeling, which is then used to interpret the seismic data. Individual polarity reversed reflectors within the stratigraphic column drilled are linked to reduction in P-wave velocity and bulk density. Those reflectors (and associated reflection packages) are accompanied by distinct and systematic changes in sediment porosity, magnetic susceptibility, and electrical resistivity. Overall, the sediments at drill site GeoB22605 (MeBo-17) represent the younger (upper) levee sequence of the channel, that has been eroded at drill site GeoB22603 (MeBo-16). Splicing seismic data across the channel from the East (MeBo-16) to the West (MeBo-17) demonstrates the continuation of reflectors underneath the channel. The upper ∼50 m below seafloor (mbsf) at site MeBo-16 do not stratigraphically belong to the same sequence of the (deeper) levee-deposits. Above the marked erosional unconformity, sediments at Site MeBo-16 are likely derived by a mixture of repeated slump-events (identified as seismically transparent units) interbedded with hemi-pelagic sedimentation. Similarly, sediments within the upper ∼20 mbsf at Site MeBo-17 are not stratigraphically the same levee-deposits, but are derived by a mixture of slump-events (also seen in the marked seafloor amphitheatre architecture of a large failure complex extending further upslope) and hemi-pelagic sedimentation. All observations combined show that the seismically observed stratigraphic pattern represents a reflectivity sequence mostly driven by variations in density (porosity) and correspondingly by changes in P-wave velocity and electrical resistivity. All observations from the geophysical log- and core, as well as geochemical data do show no evidence for the presence of any significant gas hydrates within the drilled/cored sequences.

Over the last two decades sea bed drilling technology has proven to provide a valuable complement to the services of classical drill ships. Especially for shallow drillings up to 200 mbsf and when working in remote areas difficult to access, sea bed drill rigs are a cost-effective alternative. Recent developments especially concerning borehole logging techniques add to the capabilities of sea bed drilling technology.The MARUM-MeBo is a robotic drilling system that is developed since 2004 at the MARUM Center for Marine Environmental Sciences at the University of Bremen (Freudenthal and Wefer, 2013). The drill rig is deployed on the sea bed and remotely controlled from the vessel. It is used for core drilling in soft sediments as well as hard rocks in the deep sea. Especially since an upgrade in 2007/2008 for the use of wireline drilling technique, the first-generation drill rig MARUM-MeBo70 with a drilling capacity of about 70 m was successfully deployed on more than 15 research expeditions. Since 2014 the second-generation drill rig MARUM-MeBo200 with an increased drilling capacity of up to 200 m below sea floor is successfully in operation.In this presentation we focus on results of three recent drilling campaigns, exemplifying the exploitation of the potential of the sea bed drilling technology:In early 2017 the MeBo70 was deployed from the ice breaking vessel RV POLARSTERN on the West Antarctic shelf (Gohl et al., 2017), an area difficult to access by a drill ship. We were able to recover a sedimentary sequence of the upper Cretaceous time period as one of the very few terrigenous records from this time in Antarctica. This sequence indicates that about 92 to 83 Mio years ago at a paleolatitude of about 82°S this area was covered by a temperate coastal rain forest, making any Antarctic ice sheet formation at this time period unlikely (Klages et al., in press). Also, in 2017 the MeBo70 was deployed in the Arctic off Svalbard. Next to coring a temperature probe was used to assess in situ temperatures and local geothermal gradients (Riedel et al. 2018). Combining these temperature data with the porewater geochemistry of the drilled cores Wallmann et al (2018) were able to prove the effect of isostatic rebound after deglaciation on gas hydrate dissociation. In late 2017 the MeBo200 was deployed in the Black Sea. Geophysical borehole log data of P-wave velocity, electrical resistivity, and spectral gamma ray were combined with core-derived physical properties of porosity, magnetic susceptibility, and bulk density and compared with seismic data of the region (Riedel et al., in press). This study shows the potential of core-log seismic integration for shallow drilling campaigns conducted with a sea bed drill rig. References:Freudenthal, T and Wefer, G (2013) Geoscientific Instrumentation, Methods and Data Systems, 2(2). 329-337. doi:10.5194/gi-2-329-2013Gohl, K, et al. (2017) Geochemistry, Geophysics, Geosystems, 18, 4235–4250. https://doi.org/10.1002/2017GC007081Klages, JP et al. (in press) Nature, 2019-10-14805BRiedel, M et al. (2018) Geochemistry, Geophysics, Geosystems, 19, 1165–1177. doi:10.1002/2017GC007288Riedel, M et al. (in press) Marine and Petroleum Geology, doi.org/10.1016/j.marpetgeo.2019.104192Wallmann, K et al. (2018) Nature Communications, 9:83, DOI: 10.1038/s41467-017-02550-9

We report on the geochemistry of hydrocarbons and pore waters down to 62.5 mbsf, collected by drilling with the MARUM‐MeBo70 and by gravity coring at the Lunde pockmark in the Vestnesa Ridge. Our data document the origin and transformations of volatiles feeding gas emissions previously documented in this region. Gas hydrates are present where a fracture network beneath the pockmark focusses migration of thermogenic hydrocarbons characterized by their C1/C2+ and stable isotopic compositions (δ2H‐CH4, δ13C‐CH4). Measured geothermal gradients (~80°C km‐1) and known formation temperatures (>70°C) suggest that those hydrocarbons are formed at depths >800 mbsf. A combined analytical/modeling approach, including concentration and isotopic mass balances, reveals that pockmark sediments experience diffuse migration of thermogenic hydrocarbons. However, at sites without channeled flow this appears to be limited to depths > ~50 mbsf. At all sites we document a contribution of microbial methanogenesis to the overall carbon cycle that includes a component of secondary carbonate reduction (CR) – i.e. reduction of dissolved inorganic carbon (DIC) generated by anaerobic oxidation of methane (AOM) in the uppermost methanogenic zone. AOM and CR rates are spatially variable within the pockmark and are highest at high‐flux sites. These reactions are revealed by 13C‐DIC depletions at the sulfate‐methane interface at all sites. However, 13C‐CH4 depletions are only observed at the low methane flux sites because changes in the isotopic composition of the overall methane pool are masked at high‐flux sites. 13C‐depletions of TOC suggest that at seeps sites, methane‐derived carbon is incorporated into de novo synthesized biomass.

We emphasize the importance of marine silicate weathering (MSiW) reactions in anoxic sediment as fundamental in generating alkalinity and cations needed for carbonate precipitation and preservation along continental margins. We use a model that couples thermodynamics with aqueous geochemistry to show that the CO2 released during methanogenesis results in a drop in pH to 6.0; unless these protons are buffered by MSiW, carbonate minerals will dissolve. We present data from two regions: the India passive margin and the active subduction zone off Japan, where ash and/or rivers supply the reactive silicate phase, as reflected in strontium isotope data. Offshore India and Korea, alteration of continent-derived silicates results in pore water enriched in radiogenic 87Sr, with 87Sr/86Sr ratios as high as 0.7095 and 0.7104, respectively. Off Japan, strontium in pore water influenced by ash alteration is depleted in 87Sr, with 87Sr/86Sr as low as 0.7065. Carbonate minerals formed by alkalinity and cations generated through MSiW carry these strontium isotopic signals, and are typically dolomite, siderite, and Fe-rich calcite. These contrast with the aragonite and high-magnesium calcite that form during anaerobic oxidation of methane and incorporate the coeval seawater 87Sr/86Sr signal. We show that MSiW is necessary for authigenic carbonate formation and preservation along continental margins, which remove carbon from Earth’s surface at rates previously estimated to be at least 1012 mol yr−1. In addition, these authigenic carbonates are of relevance to studies of the deep biosphere, fluid flow, seismogenesis, slope stability, and reservoir characteristics.

Our study presents a basin-scale 3D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin re-construction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics and associated multi-stage fault development. The resulting 3D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (> 80 vol. %) at the base of the gas hydrate stability zone (GHSZ), is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intra-salt mini-basins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upwards to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ∼3,256 Mt of gas hydrate which is equivalent to ∼340 Mt of carbon (∼7 x 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

Highlights • We present a 5 myr record of biogeochemical cycling in a Cretaceous upwelling area. • A novel quantitative approach for the evaluation of Fe speciation proxies was applied. • Ferruginous proxy signature reflects intense chemical weathering rather than anoxia. • Water column redox conditions evolved from oxic to nitrogenous to euxinic before OAE2. • Smaller seawater nitrate inventory facilitated sedimentary H2S release and euxinia. Abstract Oceanic Anoxic Events (OAEs) in Earth's history are regarded as analogues for current and future ocean deoxygenation, potentially providing information on its pacing and internal dynamics. In order to predict the Earth system's response to changes in greenhouse gas concentrations and radiative forcing, a sound understanding of how biogeochemical cycling differs in modern and ancient marine environments is required. Here, we report proxy records for iron (Fe), sulfur and nitrogen cycling in the Tarfaya upwelling system in the Cretaceous Proto-North Atlantic before, during and after OAE2 (∼93 Ma). We apply a novel quantitative approach to sedimentary Fe speciation, which takes into account the influence of terrigenous weathering and sedimentation as well as authigenic Fe (non-terrigenous, precipitated onsite) rain rates on Fe-based paleo-redox proxies. Generally elevated ratios of reactive Fe (i.e., bound to oxide, carbonate and sulfide minerals) to total Fe (FeHR/FeT) throughout the 5 million year record are attributed to transport-limited chemical weathering under greenhouse climate conditions. Trace metal and nitrogen isotope systematics indicate a step-wise transition from oxic to nitrogenous to euxinic conditions over several million years prior to OAE2. Taking into consideration the low terrigenous sedimentation rates in the Tarfaya Basin, we demonstrate that highly elevated FeHR/FeT from the mid-Cenomanian through OAE2 were generated with a relatively small flux of additional authigenic Fe. Evaluation of mass accumulation rates of reactive Fe in conjunction with the extent of pyritization of reactive Fe reveals that authigenic Fe and sulfide precipitation rates in the Tarfaya Basin were similar to those in modern upwelling systems. Because of a smaller seawater nitrate inventory, however, chemolithoautotrophic sulfide oxidation with nitrate was less efficient in preventing hydrogen sulfide release into the water column. As terrigenous weathering and sediment flux determine how much authigenic Fe is required to generate an anoxic euxinic or ferruginous proxy signature, we emphasize that both have to be taken into account when interpreting Fe-based paleo-redox proxies.

Periodic changes in sediment composition are usually ascribed to insolation forcing controlled by Earth’s orbital parameters. During the Cretaceous Thermal Maximum at 97–91 Myr ago (Ma), a 37–50-kyr-long cycle that is generally believed to reflect obliquity forcing dominates the sediment record. Here, we use a numerical ocean model to show that a cycle of this length can be generated by marine biogeochemical processes without applying orbital forcing. According to our model, the restricted proto-North Atlantic and Tethys basins were poorly ventilated and oscillated between iron-rich and sulfidic (euxinic) states. The Panthalassa Basin was fertilized by dissolved iron originating from the proto-North Atlantic. Hence, it was less oxygenated while the proto-North Atlantic was in an iron-rich state and better oxygenated during euxinic periods in the proto-North Atlantic. This redox see-saw was strong enough to create significant changes in atmospheric $$p_{\mathrm {CO}_2}$$ . We conclude that most of the variability in the mid-Cretaceous ocean–atmosphere system can be ascribed to the internal redox see-saw and its response to external orbital forcing. An internal redox see-saw between the Panthalassa Basin and the proto-North Atlantic can explain cyclic changes in the sediment record throughout the Cretaceous Thermal Maximum 97 to 91 million years ago, according to simulations with a numerical ocean model.

Highlights • Amazon shelf sediments take up seawater potassium (K) due to reverse weathering. • Amazon shelf sediments release terrigenous phosphorus (P) during resuspension. • Updated estimates of sedimentary K uptake and P release on Amazon shelf are presented. • Sedimentary K uptake on Amazon shelf corresponds to 13% of global riverine K input. • Sedimentary P release is ~5 times higher than dissolved P discharge of Amazon River. Abstract In this study, we identify and quantify processes that lead to sedimentary potassium (K) sequestration and phosphorus (P) release on the Amazon shelf. To this end, seven short sediment cores were recovered from the Amazon shelf during R/V Meteor cruise M147. All of the sediment cores investigated in this study are characterized by elevated K to aluminum (Al) ratios compared to Amazon riverine suspended matter, which indicates that seawater K+ is incorporated into the solid phase on the entire Amazon shelf. Pore water silica (Si) profiles are characterized by irregularly increasing concentrations and plateaus, thus, deviating from the asymptotic shape that is typically found in continental margin sediments. At one site, a dissolved Si plateau coincides with a K+ minimum suggesting that these solutes are incorporated into authigenic minerals, a process referred to as reverse weathering. Previous flux estimates for elements that participate in reverse weathering on the Amazon shelf were derived from pore water diffusive fluxes, reaction rates estimated from sediment incubations and solid phase extractions. In this study, we took an alternative approach, which is based on the concentration difference between shelf sediments and river suspended particles. The resulting K flux due to reverse weathering of 1.7 ∙ 1011 mol yr−1 is in agreement with previous estimates and corresponds to 13% of the global riverine dissolved K+ input. Previous studies demonstrated that Amazon riverine particulate P is partly solubilized on the Amazon shelf. However, these results are exclusively based on sediment data close to the river mouth and no distinction between terrestrial and marine sediment components was made. Here, we quantify P release from Amazon shelf sediments by comparing terrestrial P concentrations in shelf sediments with P concentrations in river suspended particles. The resulting solubilized P flux of 2.2 ∙ 1010 mol yr−1 is about five to six times higher than previous estimates and about seven times the Amazon riverine dissolved P discharge. The magnitudes of the presented fluxes imply that the alteration of riverine shelf sediments significantly affects the mean concentrations of dissolved K+ and P in the global ocean.

Highlights • MeBo drilling in Danube fan down to 147 m recovered limnic to marine deposits. • Molecular and stable isotope characterization of light hydrocarbons, CO2, and H2O. • H and O isotopic compositions of pore water reflect paleoclimate variations. • Isotope relations prove microbial carbonate reduction as major methanogenic pathway. • Control of δ2H–CH4 by δ2H–H2O may lead to misinterpretation of methanogenic paths. Abstract We report on the geochemistry of light hydrocarbons and pore water in sediments down to 147 m below seafloor (mbsf), at two sites within the gas hydrate stability field of the Danube deep-sea fan, Black Sea. Sediments were drilled with MARUM-MeBo200 and comprise the transition from limnic to the recent marine stage. Stable C/N ratios (mean 5.1 and 5.6) and δ13C-Corg values (mean −25.8‰ V-PDB) suggest relatively uniform bulk organic matter compositions. In contrast, pore water δ2H and δ18O values varied considerably from approx. −120‰ to −30‰ V-SMOW and from −15‰ to −3‰ V-SMOW, respectively. These data pairs plot close to the ‘Global Meteoric Water Line’ and indicate paleo temperature variations. Depletions of pore water in 2H and 18O below 40 mbsf indicate low temperatures and likely reflect conditions during (the) last glacial period(s). Methane was much more abundant than the only other hydrocarbons found in notable concentrations, ethane and propane ((C1/(C2+C3) ≥20,000). Relatively constant δ13C–CH4 (~−70‰ V-PDB) and δ13C–C2H6 (~−52‰ V-PDB) values with depth indicate that methane and ethane are predominantly of microbial origin and that their formation was not limited by carbon availability. In contrast, δ2H–CH4 values varied in a large range (approx. −310 to −240‰ V-SMOW) with depth and positively correlated with trends observed for δ2H–H2O. Isotope separations (Δδ13C(CH4–CO2), Δδ2H(CH4–H2O)) substantiate that microbial carbonate reduction (CR) is the prevalent methanogenic pathway throughout the sediments irrespective of their geochemical history. Remarkably, in δ13C–CH4 – δ2H–CH4 diagrams widely used, samples characterized by δ2H–CH4 values more negative than approx. −250‰ plot out of the field assigned for pure CR. We conclude that assignments of microbial methanogenic pathways based on classical interpretations of δ13C–CH4 – δ2H–CH4 pairs can lead to misinterpretations, as severe 2H-depletions of methane formed through microbial CR can result from 2H-depletions of the pore water generated during low-temperature climatic periods.

Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

A diagenetic model is used to simulate the diagenesis and burial of particulate organic carbon (C org ) and phosphorus (P) in marine sediments underlying anoxic versus oxic bottom waters. The latter are physically mixed by animals moving through the surface sediment (bioturbation) and ventilated by burrowing, tube-dwelling organisms (bioirrigation). The model is constrained using an empirical database including burial ratios of C org with respect to organic P (C org :P org ) and total reactive P (C org :P reac ), burial efficiencies of C org and P org , and inorganic carbon-to-phosphorus regeneration ratios. If P org is preferentially mineralized relative to C org during aerobic respiration, as many previous studies suggest, then the simulated P org pool is found to be completely depleted. A modified model that incorporates the redox-dependent microbial synthesis of polyphosphates and P org (termed the microbial P pump) allows preferential mineralization of the bulk P org pool relative to C org during both aerobic and anaerobic respiration and is consistent with the database. Results with this model show that P burial is strongly enhanced in sediments hosting fauna. Animals mix highly labile P org away from the aerobic sediment layers where mineralization rates are highest, thereby mitigating diffusive PO 4 3− fluxes to the bottom water. They also expand the redox niche where microbial P uptake occurs. The model was applied to a hypothetical shelf setting in the early Paleozoic; a time of the first radiation of benthic fauna. Results show that even shallow bioturbation at that time may have had a significant impact on P burial. Our model provides support for a recent study that proposed that faunal radiation in ocean sediments led to enhanced P burial and, possibly, a stabilization of atmospheric O 2 levels. The results also help to explain C org :P org ratios in the geological record and the persistence of P org in ancient marine sediments.

We have developed and employed an Earth system model to explore the forcings of atmospheric pCO2 change and the chemical and isotopic evolution of seawater over the last glacial cycle. Concentrations of dissolved phosphorus (DP), reactive nitrogen, molecular oxygen, dissolved inorganic carbon (DIC), total alkalinity (TA), 13C-DIC, and 14C-DIC were calculated for 24 ocean boxes. The bi-directional water fluxes between these model boxes were derived from a 3-D circulation field of the modern ocean (Opa 8.2, NEMO) and tuned such that tracer distributions calculated by the box model were consistent with observational data from the modern ocean. To model the last 130 kyr, we employed records of past changes in sea-level, ocean circulation, and dust deposition. According to the model, about half of the glacial pCO2 drawdown may be attributed to marine regressions. The glacial sea-level low-stands implied steepened ocean margins, a reduced burial of particulate organic carbon, phosphorus, and neritic carbonate at the margin seafloor, a decline in benthic denitrification, and enhanced weathering of emerged shelf sediments. In turn, low-stands led to a distinct rise in the standing stocks of DIC, TA, and nutrients in the global ocean, promoted the glacial sequestration of atmospheric CO2 in the ocean, and added 13C- and 14C-depleted DIC to the ocean as recorded in benthic foraminifera signals. The other half of the glacial drop in pCO2 was linked to inferred shoaling of Atlantic meridional overturning circulation and more efficient utilization of nutrients in the Southern Ocean. The diminished ventilation of deep water in the glacial Atlantic and Southern Ocean led to significant 14C depletions with respect to the atmosphere. According to our model, the deglacial rapid and stepwise rise in atmospheric pCO2 was induced by upwelling both in the Southern Ocean and subarctic North Pacific and promoted by a drop in nutrient utilization in the Southern Ocean. The deglacial sea-level rise led to a gradual decline in nutrient, DIC, and TA stocks, a slow change due to the large size and extended residence times of dissolved chemical species in the ocean. Thus, the rapid deglacial rise in pCO2 can be explained by fast changes in ocean dynamics and nutrient utilization whereas the gradual pCO2 rise over the Holocene may be linked to the slow drop in nutrient and TA stocks that continued to promote an ongoing CO2 transfer from the ocean into the atmosphere.

The accumulation of gas hydrates in marine sediments is essentially controlled by the accumulation of particulate organic carbon (POC) which is microbially converted into methane, the thickness of the gas hydrate stability zone (GHSZ) where methane can be trapped, the sedimentation rate (SR) that controls the time that POC and the generated methane stays within the GHSZ, and the delivery of methane from deep-seated sediments by ascending pore fluids and gas into the GHSZ. Recently, Wallmann et al. (2012) presented transfer functions to predict the gas hydrate inventory in diffusion-controlled geological systems based on SR, POC and GHSZ thickness for two different scenarios: normal and full compacting sediments. We apply these functions to global data sets of bathymetry, heat flow, seafloor temperature, POC input and SR, estimating a global mass of carbon stored in marine methane hydrates from 3 to 455 Gt of carbon (GtC) depending on the sedimentation and compaction conditions. The global sediment volume of the GHSZ in continental margins is estimated to be 60–67 × 1015 m3, with a total of 7 × 1015 m3 of pore volume (available for GH accumulation). However, seepage of methane-rich fluids is known to have a pronounced effect on gas hydrate accumulation. Therefore, we carried out a set of systematic model runs with the transport-reaction code in order to derive an extended transfer function explicitly considering upward fluid advection. Using averaged fluid velocities for active margins, which were derived from mass balance considerations, this extended transfer function predicts the enhanced gas hydrate accumulation along the continental margins worldwide. Different scenarios were investigated resulting in a global mass of sub-seafloor gas hydrates of ~ 550 GtC. Overall, our systematic approach allows to clearly and quantitatively distinguish between the effect of biogenic methane generation from POC and fluid advection on the accumulation of gas hydrate, and hence, provides a simple prognostic tool for the estimation of large-scale and global gas hydrate inventories in marine sediments.

Oxygen minimum zones (OMZs) that impinge on continental margins favor the release of phosphorus (P) from the sediments to the water column, enhancing primary productivity and the maintenance or expansion of low-oxygen waters. A comprehensive field program in the Peruvian OMZ was undertaken to identify the sources of benthic P at six stations, including the analysis of particles from the water column, surface sediments, and pore fluids, as well as in situ benthic flux measurements. A major fraction of solid-phase P was bound as particulate inorganic P (PIP) both in the water column and in sediments. Sedimentary PIP increased with depth in the sediment at the expense of particulate organic P (POP). The ratio of particulate organic carbon (POC) to POP exceeded the Redfield ratio both in the water column (202 ± 29) and in surface sediments (303 ± 77). However, the POC to total particulate P (TPP = POP + PIP) ratio was close to Redfield in the water column (103 ± 9) and in sediment samples (102 ± 15). This suggests that the relative burial efficiencies of POC and TPP are similar under low-oxygen conditions and that the sediments underlying the anoxic waters on the Peru margin are not depleted in P compared to Redfield. Benthic fluxes of dissolved P were extremely high (up to 1.04 ± 0.31 mmol m−2 d−1), however, showing that a lack of oxygen promotes the intensified release of dissolved P from sediments, whilst preserving the POC / TPP burial ratio. Benthic dissolved P fluxes were always higher than the TPP rain rate to the seabed, which is proposed to be caused by transient P release by bacterial mats that had stored P during previous periods when bottom waters were less reducing. At one station located at the lower rim of the OMZ, dissolved P was taken up by the sediments, indicating ongoing phosphorite formation. This is further supported by decreasing porewater phosphate concentrations with sediment depth, whereas solid-phase P concentrations were comparatively high.

An edited version of this paper was published by AGU. Copyright 2018 American Geophysical Union. Source at https://doi.org/10.1002/2017GC007288. During expedition MARIA S. MERIAN MSM57/2 to the Svalbard margin offshore Prins Karls Forland, the seafloor drill rig MARUM‐MeBo70 was used to assess the landward termination of the gas hydrate system in water depths between 340 and 446 m. The study region shows abundant seafloor gas vents, clustered at a water depth of ∼400 m. The sedimentary environment within the upper 100 m below seafloor (mbsf) is dominated by ice‐berg scours and glacial unconformities. Sediments cored included glacial diamictons and sheet‐sands interbedded with mud. Seismic data show a bottom simulating reflector terminating ∼30 km seaward in ∼760 m water depth before it reaches the theoretical limit of the gas hydrate stability zone (GHSZ) at the drilling transect. We present results of the first in situ temperature measurements conducted with MeBo70 down to 28 mbsf. The data yield temperature gradients between ∼38°C km−1 at the deepest site (446 m) and ∼41°C km−1 at a shallower drill site (390 m). These data constrain combined with in situ pore‐fluid data, sediment porosities, and thermal conductivities the dynamic evolution of the GHSZ during the past 70 years for which bottom water temperature records exist. Gas hydrate is not stable in the sediments at sites shallower than 390 m water depth at the time of acquisition (August 2016). Only at the drill site in 446 m water depth, favorable gas hydrate stability conditions are met (maximum vertical extent of ∼60 mbsf); however, coring did not encounter any gas hydrates.

Carbon cycling and fluid seepage in marine sediments over the late Quaternary were investigated at a now-extinct pockmark located in a mega-pockmark field in the SW Xisha Uplift (NW South China Sea). Measured particulate organic carbon (POC) content, and porewater sulfate (SO4 2-), dissolved inorganic carbon (DIC) concentrations and δ34S-SO4 2- distributions were used to constrain a non-steady-state reaction-transport model and quantify POC mineralization rates as well as estimate the time when fluid flow ceased at the investigated pockmark. An increase in POC content and δ34S-SO4 2- and a decrease in sulfate concentrations in the upper ca. 2m at the pockmark and a reference core implied an increase in the flux and reactivity of organic matter during the early Holocene around 10kyrB. P. caused by enhanced primary productivity during the strengthened southwestern summer monsoon. These features were simulated with the model assuming a Holocene increase in POC flux and reactivity. Subsequently, starting from an initial condition reminiscent of a modern active cold seep (Hydrate Ridge), hindcast simulations showed that fluid seepage at the pockmark ceased ca. 39kyr ago. This corresponds to a relative sea level high-stand, which is believed to be associated with gas hydrate stabilization. The non-steady-state model presented in this contribution can also be used to constrain the time when fluid seepage ceased at other presently extinct cold seeps when suitable sediment and porewater data are available.

Literature data on benthic dissolved iron (DFe) fluxes (µmol m−2 d−1), bottom water oxygen concentrations (O2BW, μM), and sedimentary carbon oxidation rates (COX, mmol m−2 d−1) from water depths ranging from 80 to 3700 m were assembled. The data were analyzed with a diagenetic iron model to derive an empirical function for predicting benthic DFe fluxes: inline image where γ (= 170 µmol m−2 d−1) is the maximum flux for sediments at steady state located away from river mouths. This simple function unifies previous observations that COX and O2BW are important controls on DFe fluxes. Upscaling predicts a global DFe flux from continental margin sediments of 109 ± 55 Gmol yr−1, of which 72 Gmol yr−1 is contributed by the shelf ( 2000 m) of 41 ± 21 Gmol yr−1 is unsupported by empirical data. Previous estimates of benthic DFe fluxes derived using global iron models are far lower (approximately 10–30 Gmol yr−1). This can be attributed to (i) inadequate treatment of the role of oxygen on benthic DFe fluxes and (ii) improper consideration of continental shelf processes due to coarse spatial resolution. Globally averaged DFe concentrations in surface waters simulated with the intermediate-complexity University of Victoria Earth System Climate Model were a factor of 2 higher with the new function. We conclude that (i) the DFe flux from marginal sediments has been underestimated in the marine iron cycle and (ii) iron scavenging in the water column is more intense than currently presumed.

Carbon cycling in Peruvian margin sediments (11° S and 12° S) was examined at 16 stations from 74 m on the inner shelf down to 1024 m water depth by means of in situ flux measurements, sedimentary geochemistry and modeling. Bottom water oxygen was below detection limit down to ca. 400 m and increased to 53 μM at the deepest station. Sediment accumulation rates and benthic dissolved inorganic carbon fluxes decreased rapidly with water depth. Particulate organic carbon (POC) content was lowest on the inner shelf and at the deep oxygenated stations (< 5%) and highest between 200 and 400 m in the oxygen minimum zone (OMZ, 15–20%). The organic carbon burial efficiency (CBE) was unexpectedly low on the inner shelf (< 20%) when compared to a global database, for reasons which may be linked to the frequent ventilation of the shelf by oceanographic anomalies. CBE at the deeper oxygenated sites was much higher than expected (max. 81%). Elsewhere, CBEs were mostly above the range expected for sediments underlying normal oxic bottom waters, with an average of 51 and 58% for the 11° S and 12° S transects, respectively. Organic carbon rain rates calculated from the benthic fluxes alluded to a very efficient mineralization of organic matter in the water column, with a Martin curve exponent typical of normal oxic waters (0.88 ± 0.09). Yet, mean POC burial rates were 2–5 times higher than the global average for continental margins. The observations at the Peruvian margin suggest that a lack of oxygen does not affect the degradation of organic matter in the water column but promotes the preservation of organic matter in marine sediments.

Shallow gas migration along hydrocarbon wells constitutes a potential methane emission pathway that currently is not recognized in any regulatory framework or greenhouse gas inventory. Recently, the first methane emission measurements at three abandoned offshore wells in the Central North Sea (CNS) were conducted showing that considerable amounts of biogenic methane originating from shallow gas accumulations in the overburden of deep reservoirs were released by the boreholes. Here, we identify numerous wells poking through shallow gas pockets in 3-D seismic data of the CNS indicating that about one-third of the wells may leak, potentially releasing a total of 3–17 kt of methane per year into the North Sea. This poses a significant contribution to the North Sea methane budget. A large fraction of this gas (∼42%) may reach the atmosphere via direct bubble transport (0–2 kt yr–1) and via diffusive exchange of methane dissolving in the surface mixed layer (1–5 kt yr–1), as indicated by numerical modeling. In the North Sea and in other hydrocarbon-prolific provinces of the world shallow gas pockets are frequently observed in the sedimentary overburden and aggregate leakages along the numerous wells drilled in those areas may be significant.

Monthly time-series data (1998–2009) of bottom water oxygen, nitrate and nitrite concentrations from the outer shelf (150 m water depth) in the oxygen minimum zone offshore Peru were coupled to a layered biogeochemical sediment model to investigate benthic-pelagic coupling over multi-annual time scales. The model includes the mineralization of four reactive pools of particulate organic carbon (POC) with lifetimes of 0.13, 1.3, 20, and 1700 year that were constrained using empirical data. Total POC rain rates to the seafloor were derived from satellite based estimates of primary production. Solute fluxes and concentrations in sediment porewater showed highly dynamic behavior over the course of a typical year. Conversion of fixed N to N2 by denitrification varied from 1.1 mmol m−2 d−1 of N in winter to 1.8 mmol m−2 d−1 of N in summer with a long term mean N loss for the shelf of 1.5 mmol m−2 d−1 of N. Fixed N loss across the whole time-series agreed very well with a previously-published vertically-integrated sediment model for coupling the benthic and pelagic N cycle in regional and global models. Dissimilatory nitrate reduction to ammonium (DNRA) emerges as a major process in the benthic N cycle, producing on average 1.9 mmol m−2 d−1 of ammonium: more than twice the rate of ammonification of organic nitrogen. The model predicts sulfide emissions from the sediment of up to 1 mmol m−2 d−1 when POC rain rate exceeds 20 mmol m−2 d−1, in agreement with past observations of benthic sulfide fluxes and sulfide plume distributions in the water column. This study demonstrates that sediments on the Peruvian shelf are not static repositories that are independent of changes taking place in the water column. Our results strongly suggest the shelf sediments must exert an important feedback on biogeochemical processes in the overlying waters, and should be considered in regional model studies.

A simple earth system model is developed to simulate global carbon and phosphorus cycling over the late Quaternary. It is focused on the geological cycling of C and P via continental weathering, volcanic and metamorphic degassing, hydrothermal processes and burial at the seabed. A simple ocean model is embedded in this geological model where the global ocean is represented by surface water, thermocline and deep water boxes. Concentrations of dissolved phosphorus, dissolved inorganic carbon, and total alkalinity are calculated for each box. The partial pressure of CO2 in the atmosphere (pCO(2A)) is determined by exchange processes with the surface ocean and the continents. It serves as key prognostic model variable and is assumed to govern surface temperatures and global sea-level. The model is formulated as autonomous system, in which the governing equations have no explicit time-dependence. For certain parameter values, the model does not converge towards a steady-state but develops stable self-sustained oscillations. These free oscillations feature pCO(2A) minima and maxima consistent with the ice-core record when vertical mixing in the ocean is allowed to vary in response to pCO(2A)-controlled temperature change. A stable 100-kyr cycle with a rapid transition from glacial to interglacial conditions is obtained when additional non-linear equations are applied to calculate deep ocean mixing, iron fertilization and the depth of organic matter degradation as function of pCO(2A)-controlled surface temperature. The delta C-13 value of carbon in the ocean/atmosphere system calculated in these model runs is consistent with the benthic delta C-13 record. However, the simulated C-13 depletion in the glacial ocean is not driven by the decline in terrestrial carbon stocks but by sea-level change controlling the rates of organic carbon burial and weathering at continental margins. The pCO(2A)-and delta C-13 oscillations develop without any form of external Milankovitch forcing. They are induced and maintained by sea-level change generating persistent imbalances in the marine carbon and phosphorus budgets. Stable oscillations are also obtained when sea-level change is allowed to lag temperature with a realistic time scale for ice-sheet adjustment

The isotopic composition of Phanerozoic marine sediments provides important information about changes in seawater chemistry. In particular, the radiogenic strontium isotope (87Sr/86Sr) system is a powerful tool for constraining plate tectonic processes and their influence on atmospheric CO2 concentrations. However, the 87Sr/86Sr isotope ratio of seawater is not sensitive to temporal changes in the marine strontium (Sr) output flux, which is primarily controlled by the burial of calcium carbonate (CaCO3) at the ocean floor. The Sr budget of the Phanerozoic ocean, including the associated changes in the amount of CaCO3 burial, is therefore only poorly constrained. Here, we present the first stable isotope record of Sr for Phanerozoic skeletal carbonates, and by inference for Phanerozoic seawater (δ88/86Srsw), which we find to be sensitive to imbalances in the Sr input and output fluxes. This δ88/86Srsw record varies from ∼0.25‰ to ∼0.60‰ (vs. SRM987) with a mean of ∼0.37‰. The fractionation factor between modern seawater and skeletal calcite Δ88/86Srcc-sw, based on the analysis of 13 modern brachiopods (mean δ88/86Sr of 0.176±0.016‰, 2 standard deviations (s.d.)), is -0.21‰ and was found to be independent of species, water temperature, and habitat location. Overall, the Phanerozoic δ88/86Srsw record is positively correlated with the Ca isotope record (δ44/40Casw), but not with the radiogenic Sr isotope record ((87Sr/86Sr)sw). A new numerical modeling approach, which considers both δ88/86Srsw and (87Sr/86Sr)sw, yields improved estimates for Phanerozoic fluxes and concentrations for seawater Sr. The oceanic net carbonate flux of Sr (F(Sr)carb) varied between an output of -4.7x1010mol/Myr and an input of +2.3x1010mol/Myr with a mean of -1.6x1010mol/Myr. On time scales in excess of 100Myrs the F(Sr)carb is proposed to have been controlled by the relative importance of calcium carbonate precipitates during the “aragonite” and “calcite” sea episodes. On time scales less than 20Myrs the F(Sr)carb seems to be controlled by variable combinations of carbonate burial rate, shelf carbonate weathering and recrystallization, ocean acidification, and ocean anoxia. In particular, the Permian/Triassic transition is marked by a prominent positive δ88/86Srsw-peak that reflects a significantly enhanced burial flux of Sr and carbonate, likely driven by bacterial sulfate reduction (BSR) and the related alkalinity production in deeper anoxic waters. We also argue that the residence time of Sr in the Phanerozoic ocean ranged from ∼1Myrs to ∼20Myrs.

Geochemical data (CH4, SO42−, I−, Cl−, particulate organic carbon (POC), δ13C-CH4, and δ13C-CO2) are presented from the upper 30 m of marine sediment on a tectonic submarine accretionary wedge offshore southwest Taiwan. The sampling stations covered three ridges (Tai-Nan, Yung-An, and Good Weather), each characterized by bottom simulating reflectors, acoustic turbidity, and different types of faulting and anticlines. Sulfate and iodide concentrations varied little from seawater-like values in the upper 1–3 m of sediment at all stations; a feature that is consistent with irrigation of seawater by gas bubbles rising through the soft surface sediments. Below this depth, sulfate was rapidly consumed within 5–10 m by anaerobic oxidation of methane (AOM) at the sulfate-methane transition. Carbon isotopic data imply a mainly biogenic methane source. A numerical transport-reaction model was used to identify the supply pathways of methane and estimate depth-integrated turnover rates at the three ridges. Methane gas ascending from deep layers, facilitated by thrusts and faults, was by far the dominant term in the methane budget at all sites. Differences in the proximity of the sampling sites to the faults and anticlines mainly accounted for the variability in gas fluxes and depth-integrated AOM rates. By comparison, methane produced in situ by POC degradation within the modeled sediment column was unimportant. This study demonstrates that the geochemical trends in the continental margins offshore SW Taiwan are closely related to the different geological settings.

Most of the marine biotic crises that occurred during the hot Mesozoic era have been linked to episodes of extreme warmth(1,2). Others, however, may have occurred during cooler intervals that interrupted Cretaceous greenhouse warmth(3-5). There are some indications of cooling in the late Aptian(6-8) (116-114 Myr ago), but it has not been definitively linked to biotic crisis. Here we assess the timing and magnitude of late Aptian cooling and its association with biotic crises using a suite of geochemical and micropalaeontological assessments from a marine sediment core from the North Atlantic Ocean as well as global biogeochemical modelling. Sea surface temperatures derived from the TEX86 proxy suggest that surface waters cooled by about 5 degrees C during the two million years, coincident with a positive delta C-13 excursion of approximately 2 parts per thousand in carbonates and organic carbon. Surface productivity was enhanced during this period, but the abundance of planktonic foraminifera and nannoconid phytoplankton declined. Our simulations with a biogeochemical model indicate that the delta C-13 excursion associated with the cooling could be explained by the burial of about 812,000 gigatons of carbon over 2.5 million years. About 50% of the this carbon burial occurred in the Atlantic, Southern and Tethys ocean basins. We conclude that global cooling during greenhouse conditions can cause perturbations to marine ecosystems and biogeochemical cycles at scales comparable to those associated with global warming

Seafloormethane emission from the Quepos Slide on the submarine segment of the Costa Rica fore-arc margin was estimated by extrapolating flux measurements from individual seeps to the total area covered by bacterial mats. This approach is based on the combination of detailed mapping to determine the abundance of seeps and the application of a numerical model to estimate the amount of benthic methane fluxes. Model results suggest that the majority of the studied seeps transport rather limited amount of methane (on average: *177 lmol cm-2 a-1) into the water column due to moderate upward advection, allowing for intense anaerobic oxidation of methane (AOM; on average: 53 % of the methane flux is consumed). Depth-integrated AOM rates (56–1,538 lmol CH4 cm-2 a-1) are comparable with values reported from other active seep sites. The overall amount of dissolved methane released into the water column from the entire area covered by bacterial mats on the Quepos Slide is estimated to be about 0.28 9 106 mol a-1. This conservative estimate which relies on rather accurate determinations of seafloor methane fluxes emphasizes the potential importance of submarine slides as sites of natural methane seepage; however, at present the global extent of methane seepage from submarine slides is largely unknown.

Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ~0 to 93 µM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Nino Southern Oscillation (ENSO). Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ pre-cipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.

This study provides new estimates for the global offshore methane hydrate inventory formed due to microbial CH4 production under Quaternary and Holocene boundary conditions. A multi-1D model for particular organic carbon (POC) degradation, gas hydrate formation and dissolution is presented. The novel reaction-transport model contains an open three-phase system of two solid compounds (organic carbon, gas hydrates), three dissolved species (methane, sulfates, inorganic carbon) and one gaseous phase (free methane). The model computes time-resolved concentration profiles for all compounds by accounting for chemical reactions as well as diffusive and advective transport processes. The reaction module builds upon a new kinetic model of POC degradation which considers a down-core decrease in reactivity of organic matter. Various chemical reactions such as organic carbon decay, anaerobic oxidation of methane, methanogenesis, and sulfate reduction are resolved using appropriate kinetic rate laws and constants. Gas hydrates and free gas form if the concentration of dissolved methane exceeds the pressure, temperature, and salinity-dependent solubility limits of hydrates and/or free gas, with a rate given by kinetic parameters. Global input grids have been compiled from a variety of oceanographic, geological and geophysical data sets including a new parameterization of sedimentation rates in terms of water depth. We find prominent gas hydrate provinces offshore Central America where sediments are rich in organic carbon and in the Arctic Ocean where low bottom water temperatures stabilize methane hydrates. The world’s total gas hydrate inventory is estimated at 0.82 x 10sup13 m3 - 2.10 x 10sup15 m3 CH4 (at STP conditions) or, equivalently, 4.18–995 Gt of methane carbon. The first value refers to present day conditions estimated using the relatively low Holocene sedimentation rates; the second value corresponds to a scenario of higher Quaternary sedimentation rates along continental margins. Our results clearly show that in-situ POC degradation is at present not an efficient hydrate forming process. Significant hydrate deposits in marine settings are more likely to have formed at times of higher sedimentation during the Quaternary or as a consequence of upward fluid transport at continental margins.

The question whether large scale glaciations on Antarctica were possible in a late Mesozoic greenhouse climate such as the Late Cretaceous is an intriguing one. The most recent years have provided an increasing number of studies investigating the growth and decay of paleo-continental ice sheets on Antarctica possibly large enough to affect sea level. Since the outcome of these studies doesn't provide a basis for a conclusive decision we have performed a number of model runs using an Atmospheric General Circulation Model (AGCM) to test whether large volumes of snow might have accumulated even under Late Cretaceous greenhouse conditions. By varying orbital parameters as well as topography, and atmospheric CO2 concentrations our models indicate the possibility of an Antarctic ice shield build-up large enough to drive sea level fluctuations on the order of tens of meters within ~ 20,000 years. This is supported under the assumption of pCO2 levels < 800 ppm, low insolation, and elevated topography. The growth of a major Antarctic ice sheet would be possible on reasonable time scales. To accumulate about half the present day snow/ice volume which is required to explain the documented shifts in oxygen isotopes our model results suggest a time span between 20,000 and 80,000 years for these ice volumes to accumulate.

International audience; Four seep sites located within an ∼20 km2 area offshore Georgia (Batumi seep area, Pechori Mound, Iberia Mound, and Colkheti Seep) show characteristic differences with respect to element concentrations, and oxygen, hydrogen, strontium, and chlorine isotope signatures in pore waters, as well as impregnation of sediments with petroleum and hydrocarbon potential. All seep sites have active gas seepage, near surface authigenic carbonates and gas hydrates. Cokheti Seep, Iberia Mound, and Pechori Mound are characterized by oil-stained sediments and gas seepage decoupled from deep fluid advection and bottom water intrusion induced by gas bubble release. Pechori Mound is further characterized by deep fluid advection of lower salinity pore fluids. The Pechori Mound pore fluids are altered by mineral/water reactions at elevated temperatures (between 60 and 110 °C) indicated by heavier oxygen and lighter chlorine isotope values, distinct Li and B enrichment, and K depletion. Strontium isotope ratios indicate that fluids originate from late Oligocene strata. This finding is supported by the occurrence of hydrocarbon impregnations within the sediments. Furthermore, light hydrocarbons and high molecular weight impregnates indicate a predominant thermogenic origin for the gas and oil at Pechori Mound, Iberia Mound, and Colkheti Seep. C15+ hydrocarbons at the oil seeps are allochtonous, whereas those at the Batumi seep area are autochthonous. The presence of oleanane, an angiosperm biomarker, suggests that the hydrocarbon source rocks belong to the Maikopian Formation. In summary, all investigated seep sites show a high hydrocarbon potential and hydrocarbons of Iberia Mound, Colkheti Seep, and Pechori Mound are predominantly of thermogenic origin. However, only at the latter seep site advection of deep pore fluids is indicated.

Cretaceous anoxic events may have been triggered by massive volcanic CO2 degassing as large igneous provinces (LIPs) were emplaced on the seafloor. Here, we present a comprehensive modeling study to decipher the marine biogeochemical consequences of enhanced volcanic CO2 emissions. A biogeochemical box model has been developed for transient model runs with time-dependent volcanic CO2 forcing. The box model considers continental weathering processes, marine export production, degradation processes in the water column, the rain of particles to the seafloor, benthic fluxes of dissolved species across the seabed, and burial of particulates in marine sediments. The ocean is represented by twenty-seven boxes. To estimate horizontal and vertical fluxes between boxes, a coupled ocean–atmosphere general circulation model (AOGCM) is run to derive the circulation patterns of the global ocean under Late Cretaceous boundary conditions. The AOGCM modeling predicts a strong thermohaline circulation and intense ventilation in the Late Cretaceous oceans under high pCO2 values. With an appropriate choice of parameter values such as the continental input of phosphorus, the model produces ocean anoxia at low to mid latitudes and changes in marine δ13C that are consistent with geological data such as the well established δ13C curve. The spread of anoxia is supported by an increase in riverine phosphorus fluxes under high pCO2 and a decrease in phosphorus burial efficiency in marine sediments under low oxygen conditions in ambient bottom waters. Here, we suggest that an additional mechanism might contribute to anoxia, an increase in the C:P ratio of marine plankton which is induced by high pCO2 values. According to our AOGCM model results, an intensively ventilated Cretaceous ocean turns anoxic only if the C:P ratio of marine organic particles exported into the deep ocean is allowed to increase under high pCO2 conditions. Being aware of the uncertainties such as diagenesis, this modeling study implies that potential changes in Redfield ratios might be a strong feedback mechanism to attain ocean anoxia via enhanced CO2 emissions. The formation of C-enriched marine organic matter may also explain the frequent occurrence of global anoxia during other geological periods characterized by high pCO2 values.

Two volcanic ash layer dominated marine gravity cores were recovered during research cruise RV Sonne 173/3 along the Pacific margin offshore Nicaragua. Thick ash layers dominate the recovered sediments. Pore water samples of these – one incoming plate and one slope site – sediment cores have been analysed for light rare earth elements, alkalinity, sulphate, phosphate, ammonia, calcium, and manganese contents. The data provide a systematic look at changes in REE during diagenesis proceeding from open ocean sediments to highly reducing near-shore sediments. The pore water patterns of all the dissolved species mentioned above suggest that volcanic glass alteration constitutes a major source for REE release in marine sediments when low rates of anaerobic degradation of organic matter, like typical for incoming plate/open ocean sediments, prevail. Under these conditions the release of REE results in fluxes of at least 0.04 nmol La cm− 2 yr− 1 and 0.09 nmol Ce cm− 2 yr− 1.

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation. (C) 2009 Elsevier Ltd. All rights reserved.

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to similar to 650 mmol L-1 at similar to 150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle QUEST revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at similar to 60 cm sediment depth that were 0.9 degrees C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (delta D-CH4 = -170.8 parts per thousand (SMOW), delta C-13-CH4 = -61.0 parts per thousand (V-PDB), delta C-13-C2H6 = -44.0 parts per thousand (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 +/- 0.5 x 106 mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column. (C) 2009 Elsevier Ltd. All rights reserved.

Porewater data from vent sites of the northeastern shelf off Sakhalin Island, Sea of Okhotsk, exhibit bottom-water concentrations down to a sediment depth of up to 300 cm. Below this depth, solute concentrations rapidly change due to methanogenesis and anaerobic methane oxidation (AMO). The profile shapes suggest an irrigation-like process that mixes on a meter scale. At these sites active gas emanation into the overlying water column and near-surface gas hydrates are commonly observed. We propose that methane gas bubbles rise through the soft surface sediments and cause mixing of the porewater. Mathematically, the bubble-induced irrigation can be described by eddy diffusion enhancing the diffusive transport of solutes by several orders of magnitude. A 3-D numerical transport-reaction model was developed to investigate the parameters defining the mixing process, such as bubble rise velocity, tube size, tube distribution in the sediment, and ebullition frequency. Model consistency with the field data requires eddy diffusivities ⩾1 × 105 cm2/a, tube densities of >4 tubes/m2 (equivalent to a tube spacing of

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world not, vert, similar 112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate not, vert, similar 25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere–land–ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (not, vert, similar 45,000 yr) period of not, vert, similar 0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns, H.C., 2003. Evidence for rapid climate change in the Mesozoic–Palaeogene greenhouse world. The Royal Society, 361: 1885–1916.] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 × 1018 g methane carbon (δ13C = − 60 ‰), equivalent to about 10% to the total modern gas hydrate inventory, generated the δ13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over not, vert, similar 25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Controversy over the oxygen isotope composition of seawater began in the 1950's, since which time there has been no agreement over whether the oxygen isotope composition of the oceans has changed over time. Resolving this uncertainty would allow the δ18O values of demonstrably well preserved marine authigenic precipitates to be used to reconstruct surface climate trends back to early Archean times and would help towards a more quantitative description of Earth's global water cycle on geological time scales. Isotopic studies of marine carbonate and silica reveal a trend of increasing δ18O values with decreasing age since the Archean. This trend has been interpreted by some to reflect a progressive increase in seawater δ18O through time; however, it is generally accepted on the basis of ophiolite studies and theoretical considerations that seawater δ18O cannot change significantly because of the buffering effects of ocean crust alteration at mid-ocean ridges. As a result many alternative interpretations have been proposed, including meteoric alteration; warmer paleoclimates; higher seawater pH; salinity stratification and biased sampling. Here we review these interpretations in the light of an updated compilation of marine carbonate δ18O from around the world, covering the Phanerozoic and Precambrian rock records. Recent models of the geological water cycle demonstrate how long-term trends in chemical weathering and hydrothermal circulation can indeed influence the O-isotope composition of the global ocean to the extent necessary to explain the carbonate δ18O trend, with residual variation attributed to climatic fluctuations and post-depositional alteration. We present the further development of an existing model of the geological water cycle. In the model, seawater δ18O increased from about − 13.3‰ to − 0.3‰ over a period of 3.4 Ga, with average surface temperatures fluctuating between 10 °C to 33 °C, which is consistent with known biological constraints. Similar temperature variations are also obtained, although with higher starting seawater δ18O composition, when more conservative approaches are used that take into account the systematic effects of diagenetic alteration on mean calcite δ18O values. In contrast to much published opinion, the average δ18O value of ocean crust in the model remained relatively unchanged throughout all model runs. Invariable ophiolite δ18O values can, therefore, not be used as a definitive argument against changing seawater δ18O. The most likely explanation for the long-term trend in seawater δ18O invokes two stepwise increases in the ratio of high- to low-temperature fluid/rock interactions. An initial increase may have occurred close to the Archean–Proterozoic boundary, but a possibly more significant increase took place near the Proterozoic–Phanerozoic boundary. Possible explanations for extremely low seawater δ18O during the Archean include higher continental weathering rates caused by a combination of higher atmospheric pCO2 (necessarily combined with high CO2 outgassing rates), a greater abundance of relatively easily weathered volcanic rocks in greenstone belts and partial emergence of spreading ridges. The second increase may have been caused by the suppression of low-temperature overprinting of ocean crust alteration by the formation of a thick sediment cover on ridge flanks due to the emergence of shelly plankton at the beginning of the Phanerozoic. Postulated increases in spreading ridge depths since the Archean would also have enhanced the efficiency of vertical heat flux and changed the depth at which hydrothermal fluids boil, both of which would favour high- over low-temperature interactions with time.

Pore fluids from the Green Canyon Block in the northern Gulf of Mexico show distinct differences with respect to element concentrations and oxygen, hydrogen, and strontium isotope signatures. The shallowest of the three investigated sites (GC185 or Bush Hill at 540 m water depth) is interpreted as a seafloor piercing mud mound and the two deeper areas (GC415 East and West at 950 and 1050 m water depth) as gas vent and oil seep sites. All three locations accommodate near-surface gas hydrates and the sediment surface is populated with chemosynthetic communities. They are characterized by a distinct increase in salinity with depth. However, the origin of this increasing salinity is different for the GC415 sites and Bush Hill and the depth source of the fluids is considerably different for all sites. The more saline fluids of the GC415 sites result from the dissolution of halite by formation water from two different sources. The fluids of GC415 East have most likely a deeper origin (early Cenozoic or even Mesozoic) and experienced elevated temperatures leading to mineral/water reactions including mineral transformations (e.g. smectite to illite transformation) and dissolution (e.g. feldspar dissolution). This process is expressed by the heavier oxygen isotope values and distinct Li, Sr, and Ca enrichments. The fluids of GC415 West have a shallower origin which is expressed by a smaller enrichment in Li, Sr, and Ca and lighter oxygen isotopes. The fluids from Bush Hill are less saline and its fluid signature indicates intensive water/mineral interaction. Oxygen and hydrogen isotope values as well as Na/Cl and Br/Cl molar ratios suggest that the salt enrichment was caused by phase separation under sub-critical conditions. A simple heat flow model simulation suggests that sub-critical phase separation may have occurred at a depth of ∼ 1650 m at ∼ 350 °C.

The Hg distribution and some mineralogical-geochemical features of bottom sediments up to a depth of 10 m in the Deryugin Basin showed that the high and anomalous Hg contents in the Holocene deposits are confined to a spreading riftogenic structure and separate fluid vents within it. The accumulations of Hg in the the sediments were caused by its fluxes from gas and low-temperature hydrothermal vents under favorable oceanological conditions in the Holocene. The two mainly responsible for the high and anomalous Hg contents are infiltration (fluxes of hydrothermal or gas fluids from the sedimentary cover) and plume (Hg precipitation from water plumes with certain hydrochemical conditions forming above endogenous sources). The infiltration anomalies of Hg were revealed in the following environments: (1) near gas vents on the northeastern Sakhalin slope, where high Hg contents are associated only with Se and were caused by the accumulation of gases ascending from beneath the gas hydrate layer; (2) in the area of inferred occasionally operating low-temperature hydrothermal seeps in the central part of the Deryugin Basin, in which massive barite chimneys, hydrothermal Fe-Mn crusts, and anomalous contents of Mn, Ba, Zn, and Ni in sediments develop.

We developed and employed an earth system model to explore the forcings of atmospheric pCO2 change and the chemical and isotopic evolution of seawater over the last glacial cycle. Concentrations of dissolved phosphorus, reactive nitrogen, molecular oxygen, dissolved inorganic carbon (DIC), total alkalinity (TA), 13C-DIC and 14C-DIC were calculated for 24 ocean boxes. The bi-directional water fluxes between these model boxes were derived from a 3-D circulation field of the modern ocean (Opa 8.2, NEMO) and tuned such that tracer distributions calculated by the box model were consistent with observational data from the modern ocean. To model the last 130 kyr, we employed records of past changes in sea-level, ocean circulation, and dust deposition. According to the model, about half of the glacial pCO2 drawdown may be attributed to marine regressions. The glacial sea-level low-stands implied steepened ocean margins, a reduced burial of particulate organic carbon, phosphorus, and neritic carbonate at the margin seafloor, a decline in benthic denitrification, and enhanced weathering of emerged shelf sediments. In turn, they led to a distinct rise in the standing stocks of DIC, TA, and nutrients in the global ocean, promoted the glacial sequestration of atmospheric CO2 in the ocean, and added 13C- and 14C-depleted DIC to the ocean as recorded in benthic foraminifera signals. The other half of the glacial drop in pCO2 was linked to reduced deep ocean dynamics, a shoaling of Atlantic meridional overturning circulation, and a rise in iron fertilization. The increased transit time of deep waters in the glacial ocean led to significant 14C depletions with respect to the atmosphere. The deglacial rapid and stepwise rise in atmospheric pCO2 was induced by upwelling both in the Southern Ocean and subarctic North Pacific and promoted by a drop in dust-borne iron discharge to the Southern Ocean. The deglacial sea-level rise led to a gradual decline in nutrient, DIC, and TA stocks, a slow change due to the large size and extended residence times of dissolved chemical species in the ocean. Thus, the rapid deglacial rise in pCO2 was dominated by fast changes in ocean dynamics and reduced dust deposition whereas the gradual pCO2 rise over the Holocene may be linked to the slow drop in nutrient and TA stocks that continued to promote an ongoing CO2 transfer from the ocean into the atmosphere.

As a result of extensive hydrocarbon exploration, the North Sea hosts several thousand abandoned wells; many believed to be leaking methane. However, how much of this greenhouse gas is emitted into the water column and ultimately reaches the atmosphere is not known. Here, we investigate three abandoned wells at 81–93 m water depth in the Norwegian sector of the North Sea, all of which show gas seepage into the bottom water. The isotopic signature of the emanating gas points towards a biogenic origin and hence to gas pockets in the sedimentary overburden above the gas reservoirs that the wells were drilled into. Video-analysis of the seeping gas bubbles and direct gas flow measurements resolved initial bubble sizes ranging between 3.2 and 7.4 mm in diameter with a total seabed gas flow between 1 and 19 tons of CH4 per year per well. Estimated total annual seabed emissions from all three wells of ∼24 tons are similar to the natural seepage rates at Tommeliten, suggesting that leaky abandoned wells represent a significant source of methane into North Sea bottom waters. However, the bubble-driven direct methane transport into the atmosphere was found to be negligible (

A recurrent interpretation of ancient climate based on the oxygen isotopic composition of marine carbonates and cherts suggests that Earth's climate was substantially warmer in the distant past and remained so until as recently as 400 Myr ago. This interpretation is difficult to reconcile with the long-term glacial record, with evidence for modest weathering rates during most of Earth's history, with biomarker and fossil evidence for eukaryotes and even vertebrates at times of anomalously low δ18O values, and with the predicted faintness of the young Sun. We argue here, following earlier suggestions, that the low δ18O values in ancient rocks are a consequence of the low δ18O of ancient seawater. A modest increase in ocean depth with time, together with progressive increases in pelagic sedimentation on midocean ridge flanks since about 550 Ma, could account for the variation in seawater isotopic composition. The required change in ocean depth, coupled with thinning of the oceanic crust, is a natural consequence of the decline in heat flow over time. Contrary to previous assertions, such a model is not inconsistent with data from ophiolites. It seems likely that Earth's climate remained largely within Phanerozoic norms throughout the past 3.5 Ga.

During the MARGASCH cruise M52/1 in 2001 with RV Meteor we sampled surface sediments from three stations in the crater of the Dvurechenskii mud volcano (DMV, located in the Sorokin Trough of the Black Sea) and one reference station situated 15 km to the northeast of the DMV. We analysed the pore water for sulphide, methane, alkalinity, sulphate, and chloride concentrations and determined the concentrations of particulate organic carbon, carbonate and sulphur in surface sediments. Rates of anaerobic oxidation of methane (AOM) were determined using a radiotracer (14CH4) incubation method. Numerical transport-reaction models were applied to derive the velocity of upward fluid flow through the quiescently dewatering DMV, to calculate rates of AOM in surface sediments, and to determine methane fluxes into the overlying water column. According to the model, AOM consumes 79% of the average methane flux from depth (8.9 · 10+ 6 mol a− 1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9 · 10+ 6 mol a− 1. If it is assumed that all submarine mud volcanoes (SMVs) in the Black Sea are at an activity level like the DMV, the resulting seepage represents less than 0.1% of the total methane flux into this anoxic marginal sea. The new data from the DMV and previously published studies indicate that an average SMV emits about 2.0 · 10+ 6 mol a− 1 into the ocean via quiescent dewatering. The global flux of dissolved methane from SMVs into the ocean is estimated to fall into the order of 10+ 10 mol a− 1. Additional methane fluxes arise during periods of active mud expulsion and gas bubbling occurring episodically at the DMV and other SMVs